EP2950380B1 - Électrolyte pour batterie lithium-air et batterie lithium-air contenant celui-ci - Google Patents

Électrolyte pour batterie lithium-air et batterie lithium-air contenant celui-ci Download PDF

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Publication number
EP2950380B1
EP2950380B1 EP15169264.7A EP15169264A EP2950380B1 EP 2950380 B1 EP2950380 B1 EP 2950380B1 EP 15169264 A EP15169264 A EP 15169264A EP 2950380 B1 EP2950380 B1 EP 2950380B1
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EP
European Patent Office
Prior art keywords
group
electrolyte
lithium
air battery
formula
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EP15169264.7A
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German (de)
English (en)
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EP2950380A3 (fr
EP2950380A2 (fr
Inventor
Dongjoon Lee
Dongmin Im
Kihyun Kim
Taeyoung Kim
Victor Roev
Sangbok Ma
Minsik PARK
Wonsung Choi
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Samsung Electronics Co Ltd
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Samsung Electronics Co Ltd
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Priority claimed from KR1020150058273A external-priority patent/KR101758255B1/ko
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Publication of EP2950380A3 publication Critical patent/EP2950380A3/fr
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present disclosure relates to electrolytes for lithium air batteries, and lithium air batteries including the same.
  • a lithium air battery includes an anode that allows plating and stripping of lithium ions, a cathode that uses oxygen as a cathode active material and includes a catalyst for oxidizing and reducing oxygen, and a lithium ion-conductive electrolyte disposed between the cathode and the anode.
  • Lithium air batteries have a theoretical energy of about 3000 Watt-hours per kg (Wh/kg) or greater, which is equivalent to about ten times that of lithium ion batteries. Furthermore, because they are more environmentally friendly and safer in use than lithium ion batteries, lithium air batteries are increasingly being developed.
  • an electrolyte for a lithium air battery with improvement in both oxidation resistance and lithium ion solubility.
  • a lithium air battery having improved performance by using the electrolyte.
  • an electrolyte for a lithium air battery includes a compound represented by Formula 1 and a lithium salt: wherein, in Formula 1,
  • a lithium air battery includes: an anode; a cathode; and the electrolyte including a lithium salt and a compound represented by Formula 1.
  • spatially relative terms such as “beneath,” “below,” “lower,” “above,” “upper” and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the exemplary term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
  • Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
  • the oxidation resistance of the lithium ion-conductive electrolyte may have a trade-off relationship with the solubility of lithium ions, which may lower the performance of the lithium air battery.
  • an electrolyte for a lithium air battery includes a compound represented by Formula 1 and a lithium salt. wherein, in Formula 1,
  • the compound of Formula 1 may have lithium ion conductivity and good oxidation resistance, good lithium salt solubility, and good oxygen affinity.
  • R 1 and R 2 in Formula 1 may include, each independently, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, a fluoropropyl group, a difluoropropyl group, a trifluoropropyl group, a tetrafluoropropyl group, a pentafluoropropyl group, a hexafluoropropyl group, or a heptafluoropropyl group.
  • R 3 to R 17 in Formula 1 may include, each independently, a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group.
  • R 20 and R 21 may be each independently a fluorine atom, a C 1 -C 10 alkyl group that is partially or fully substituted with fluorine, or a C 6 -C 30 aryl group that is partially or fully substituted with fluorine, and the remaining R 20 or R 21 is a hydrogen atom, a unsubstituted or substituted C 1 -C 10 alkyl group, or a unsubstituted or substituted C 6 -C 30 aryl group, wherein optionally, R 20 and R 21 may form a C 3 -C 8 ring that is partially or fully substituted with fluorine.
  • R 18 and R 21 may each independently include a fluorine atom, a methyl group, an ethyl group, a propyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, a fluoropropyl group, a difluoropropyl group, a trifluoropropyl group, a tetrafluoropropyl group, a pentafluoropropyl group, a hexafluoropropyl group, or a heptafluoropropyl group, and the remaining R 18 to R 21 may be a hydrogen, a methyl group, an ethyl group, a propyl group, a flu
  • m may be in a range of 1 to 1,000, n may be in a range of 0 to 1,000, and p may be in a range of 1 to 1,000. In some other embodiments, m may be in a range of 1 to 100, n may be in a range of 0 to 100, and p may be in a range of 0 to 100. In still other embodiments, m may be in a range of 1 to 10, n may be in a range of 0 to 10, and p may be in a range of 0 to 10.
  • the compound of Formula 1 may be a compound represented by Formula 1 a or 1 b. wherein, in Formula 1 a,
  • the compound of Formula 1 may be selected from compounds represented by Formulae 2 to 5.
  • the amount of the compound of Formula 1 may be in a range of about 15 parts to about 97 parts by weight, for example about 20 parts to about 90 parts by weight based on 100 parts by weight of the total weight of the electrolyte.
  • the electrolyte may have improved oxidation resistance and improved solubility of lithium salt.
  • the compound of Formula 1 acts as a solvent for dissolving the lithium salt.
  • the lithium salt is dissolved in the compound of Formula 1.
  • the resultant acts as a source for providing lithium ions in the battery, and it facilitates movement of the lithium ions.
  • Non-limiting examples of the lithium salt include The lithium salt may include at least one selected from LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 ), wherein x and y are natural numbers, LiF, LiBr, LiCl, Lil, or LiB(C 2 O 4 ) 2 (LiBOB; lithium bis(oxalato) borate).
  • the lithium salt in the electrolyte for a lithium air battery may be a lithium sulfonimide compound.
  • the lithium sulfonimide compound may be lithium fluoroalkylsulfonimide, lithium fluoroarylsulfonimide, or lithium fluoroalkylarylsulfonimide, wherein each contains 1 to 20 carbon atoms, 1 to 16 carbon atoms, or 1 to 10 carbon atoms.
  • Non-limiting examples of the lithium sulfonimide compound include Li(FSO 2 ) 2 N, Li(CF 3 SO 2 ) 2 N, Li(C 2 F 5 SO 2 ) 2 N, LiN(C p F 2p+1 SO 2 )(C q F 2q+1 SO 2 ) (where p and q may differ and may be each independently an integer of 1 to 20), LiN((SO 2 ) 2 C p F 2p ) (where p may be an integer of 1 to 10), Li(C 6 F 5 SO 2 ) 2 N, Li(C 10 F 7 SO 2 ) 2 N, Li(C 6 F 5 SO 2 )(C 10 F 7 SO 2 )N, LiN(C 6 F 5 SO 2 )(C p F 2p+1 SO 2 ) (where p may be an integer of 1 to 10), or LiN(C 10 F 7 SO 2 )(CpF 2p+1 SO 2 ) (where p may be an integer of 1 to 10).
  • the electrolyte for a lithium air battery may further include a nonaqueous organic solvent.
  • the nonaqueous organic solvent include methylbutyl ether, diethyl ether, ethyl butyl ether, dibutyl ether, polyethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether; cyclohexanone, dioxane; dimethoxyethane, 2-methyltetrahydrofuran, 2,2-dimethyltetrahydrofuran, 2,5-dimethyltetrahydrofuran, tetrahydrofuran; dimethyl acetate, ethyl acetate, n-propyl acetate, dimethylacetate, methylpropionate, ethyl propionate; methyl formate, or ethyl formate; dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, methyl propyl carbonate, methyl prop
  • the electrolyte for a lithium air battery may further include a lithium ion-conductive polymer, in addition to the compound of Formula 1.
  • the lithium ion-conductive polymer may include polyethylene oxide, polyacrylonitrile (PAN), or polyester.
  • the compound of Formula 1 may include a fluorine atom in a selected position to improve the oxidation resistance, oxygen affinity, and salt solubility of the electrolyte.
  • oxidation resistance refers to the resistance to oxidation of the electrolyte by a potential difference at an electrode or by reaction with an oxidation product of lithium ions.
  • oxygen affinity refers to the ability of oxygen permeability of the electrolyte.
  • salt solubility refers to the solubility of the lithium salt of the electrolyte.
  • a fluorine atom or a group substituted with a fluorine atom may be directly bound to a carbon atom in the middle of a propyl group between oxygen atoms, thereby improving the oxidation resistance, oxygen affinity, and salt solubility of the electrolyte.
  • a conventional ether electrolyte may have improved oxidation resistance, but reduced lithium salt solubility, by substitution of a hydrogen atom with a fluorine atom.
  • the compound of Formula 1 may be improved both in oxidation resistance and salt solubility by the substitution, of all or some hydrogen atoms with fluorine atoms on the carbon atom in the middle of the propyl group between oxygen atoms.
  • the oxygen affinity of the electrolyte may also be improved by the compound of Formula 1.
  • a lithium air battery includes: an anode that allows plating and stripping of lithium ions; a cathode using oxygen as a cathode active material; and an electrolyte according to any of the above-described embodiments that include a lithium salt and a compound represented by Formula 1 as described above.
  • the amount of the compound of Formula 1 may be in a range of about 15 parts to about 97 parts by weight, for example about 20 parts to about 90 parts by weight based on 100 parts by weight of the total weight of the electrolyte. When the amount of the compound of Formula 1 is within this range, the electrolyte may have improved conductivity.
  • the electrolyte includes at least one selected from an ionic liquid and ionic liquid.
  • the inorganic filler may be any filler as long as the filler is commonly used in a lithium air battery.
  • the inorganic filler may be at least one selected from BaTiO 3 SiO 2 TiO 2 ZrO 2 , and zeolite.
  • the amount of the inorganic filler may be in the range of about 0.1 to about 20 parts by weight based on 100 parts by weight of the total weight of the compound of Formula 1 and a lithium salt.
  • the lithium air battery may further include a lithium ion-conductive layer disposed between the anode and the electrolyte.
  • the lithium ion-conductive layer includes an ion-conductive inorganic particle.
  • the ion-conductive inorganic particle may be at least one selected from a glassy active metal ion conductor, an amorphous active metal ion conductor, a ceramic active metal ion conductor, a glass-ceramic active metal ion conductor, or a combination thereof.
  • the ion-conductive inorganic particle may be at least one selected from Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (where 0 ⁇ x ⁇ 2 and 0 ⁇ y ⁇ 3), BaTiO 3 , Pb(Zr,Ti)O 3 (PZT) Pb 1-x La x Zr 1-y Ti y O 3 (PLZT) (where 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1),PB(Mg 3 Nb 2/3 )O 3 -PbTiO 3 (PMN-PT) HfO 2 , SrTiO 3 SnO 2 , CeO 2 , Na 2 O, MgO, NiO, CaO, BaO, ZnO, ZrO 2 , Y 2 O 3 , Al 2 O 3 , TiO 2 , SiO 2 , SiC, lithium phosphate (Li 3 PO 4 ), lithium titanium phosphate (Li x Ti y (PO 4 ) 3 (where 0 ⁇
  • the lithium air battery may further include a second electrolyte disposed between the anode and the lithium ion-conductive layer.
  • the second electrolyte may be a solid polymer electrolyte or an inorganic solid electrolyte.
  • FIG. 1 is a schematic view of a lithium air battery 10 according to an embodiment.
  • the lithium air battery 10 includes a first current collector 11, a second current collector 12, a cathode 13, an anode 14, and an electrolyte disposed between the cathode 13 and the anode 14 and including a compound of Formula 1 described above and a lithium salt (hereinafter, referred to as "first electrolyte").
  • the cathode 13 may be disposed on the first current collector 11. In the cathode 13, oxidation and reduction of oxygen used as an active material take place.
  • the anode 14 may be disposed on the second current collector 12. In the anode 14, oxidation and reduction of lithium metal take place.
  • the first electrolyte 15 may enable conduction of lithium ions between the cathode 13 and the anode 14.
  • a porous structure in a net shape or mesh shape may be used as the first and second current collectors 11 and 12 to facilitate diffusion of oxygen.
  • first and second current collectors 11 and 12 may be used as the first and second current collectors 11 and 12.
  • Materials for the first and second current collectors 11 and 12 are not particularly limited, and any appropriate material for a current collector available in the art may be used.
  • the first and second current collectors 11 and 12 may be coated with an antioxidation metal or an alloy thereof to prevent oxidation.
  • the cathode 13 that uses oxygen as a cathode active material may include a porous conductive material.
  • Any porous and conductive material for example, a porous carbonaceous material, may be used without limitations as the cathode 13.
  • Suitable porous carbonaceous materials may be carbon black, graphite, graphene, activated carbon, carbon nanotubes, and carbon fibers.
  • a metallic conductive material for example, metal fiber, metal mesh, or the like, may be used as the cathode 13.
  • metal powder of copper, silver, nickel, aluminum, or the like may be used as the cathode 13.
  • Organic conductive materials such as polyphenylene derivatives may also be used as the cathode 13. The above-listed conductive materials may be used alone or in combination.
  • the cathode 13 may further include a catalyst for facilitating oxidation or reduction of oxygen.
  • a catalyst for facilitating oxidation or reduction of oxygen include precious metal-based catalysts, such as platinum (Pt), gold (Au), silver (Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), and osmium (Os); oxide-based catalysts, such as manganese oxide, iron oxide, cobalt oxide, and nickel oxide; or organic metal-based catalysts, such as cobalt phthalocyanine. Any appropriate catalysts for oxidation and reduction of oxygen available in the art may be used.
  • the catalyst may be supported on a support.
  • the support include oxide, zeolite, clay mineral, and carbon.
  • the oxide may include at least one oxide of alumina, silica, zirconium oxide, and titanium dioxide.
  • the oxide may be an oxide that includes at least one metal selected from cerium (Ce), praseodymium (Pr), samarium (Sm), europium (Eu), terbium (Tb), thulium (Tm), ytterbium (Yb), antimony (Sb), bismuth (Bi), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb), molybdenum (Mo), and tungsten (W).
  • Non-limiting examples of the carbon include carbon black, such as Ketjen black, acetylene black, channel black, and lamp black; graphite, such as natural graphite, artificial graphite, and expanded graphite; activated carbon; and carbon fibers. Any appropriate materials available as supports in the art may be used.
  • the cathode 13 may further include a binder.
  • the binder may include a thermoplastic resin or a thermocurable resin.
  • Non-limiting examples of the binder include polyethylene, polypropylene, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), styrene-butadiene rubber, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-chlorotrifluoroethylene copolymer, an ethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, a fluorovinylidene-pentafluoro propylene copolymer, a propylene-tetrafluoroethylene copolymer, an ethylene-chlorotrifluoroethylene copolymer, a vinyl
  • the cathode 13 may be manufactured as follows. For example, a catalyst for oxidation/reduction of oxygen, a conductive material, and a binder may be mixed together, and then an appropriate solvent may be added thereto to prepare a cathode slurry. The cathode slurry may be coated and dried on a surface of the first current collector 11, optionally followed by press-molding to improve the density of the cathode 13, thereby manufacturing the cathode 13.
  • the cathode 13 may include a lithium oxide.
  • the cathode 13 may not include the catalyst for oxidation/reduction of oxygen.
  • the anode 14 may include, but is not limited to, lithium metal, a lithium metal-based alloy, or a material that allows plating and stripping of lithium ions.
  • the anode 14 may determine the capacity of the lithium air battery 10.
  • the lithium metal-based alloy may be, for example, an alloy of lithium with aluminum (Al), tin (Sn), magnesium (Mg), indium (In), calcium (Ca), germanium (Ge), antimony (Sb), bismuth (Bi), or lead (Pb).
  • the porous cathode 13 may be fully or partially impregnated with the first electrolyte 15.
  • FIG. 2 is a schematic view of a structure of a lithium air battery cell 20 according to another embodiment.
  • the lithium air battery cell 20 includes a first current collector 11, a second current collector 12, a cathode 13, an anode 14, a lithium ion-conductive layer 24 disposed between the cathode 13 and the anode 14, an electrolyte 25 (hereinafter, referred to as a first electrolyte) disposed between the cathode 13 and the lithium ion conductive layer 24 and including the compound of Formula 1 described above and a lithium salt, and a second electrolyte 26 between the anode 14 and the lithium ion-conductive layer 24.
  • a first electrolyte disposed between the cathode 13 and the lithium ion conductive layer 24 and including the compound of Formula 1 described above and a lithium salt
  • a second electrolyte 26 between the anode 14 and the lithium ion-conductive layer 24.
  • the anode 14, the second electrolyte 25, and the lithium ion-conductive layer 24 may be collectively called a protected anode.
  • the cathode 13, the anode 14, and the first electrolyte 25 in FIG. 2 correspond to the cathode 13, the anode 14, and the first electrolyte 15 in FIG. 1 , respectively, and thus detailed descriptions thereof will be omitted here.
  • the lithium ion-conductive layer 24 having lithium-ion conductivity may include an ion-conductive inorganic particle.
  • the second electrolyte 26 may be, but not limited to, a solid polymer electrolyte membrane or an inorganic solid electrolyte.
  • the polymer electrolyte membrane may be, for example, a polyethylene oxide membrane, a polyacrylonitrile membrane, or a polyester membrane.
  • the solid polymer electrolyte membrane may be prepared by mixing a lithium ion-conductive polymer and a lithium salt.
  • the lithium salt may include at least one selected from LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(CyF 2y+1 SO 2 ), wherein x and y are natural numbers, LiF, LiBr, LiCl, Lil, and LiB(C 2 O 4 ) 2 (LiBOB; lithium bis(oxalato) borate).
  • the inorganic solid electrolyte may be Cu 3 N, Li 3 N, or LiPON.
  • the second electrolyte 26 may be a lithium ion-conductive solid electrolyte membrane.
  • the lithium ion-conductive solid electrolyte may be a glass-ceramic solid electrolyte, or a laminated structure of a glass-ceramic solid electrolyte and a solid polymer electrolyte.
  • a "glass-ceramic” refers to a polycrystalline material generated through controlled crystallization of base glass. The lithium ion-conductive solid electrolyte membrane will now be described in greater detail.
  • the lithium ion-conductive solid electrolyte may include an inorganic material including lithium ion-conductive glass, a lithium ion-conductive crystal (ceramic or glass-ceramic), or a combination thereof.
  • the lithium ion-conductive solid electrolyte membrane may include an oxide, in consideration of chemical stability.
  • the lithium ion-conductive solid electrolyte includes a large amount of lithium ion-conductive crystals, a high ionic conductivity may be attainable.
  • the lithium ion-conductive solid electrolyte membrane may include about 50 wt.% or greater, about 60 wt.% or greater, or about 70 wt.% or greater of lithium ion-conductive crystals, based on the total weight of the lithium ion-conductive solid electrolyte membrane.
  • the lithium ion-conductive crystals may be lithium ion-conductive particles having a Perovskite structure, such as Li 3 N, LISICON, La 0.55 Li 0.35 TiO 3 , and the like, LiTi 2 P 3 O 12 crystals having a NASICON structure, or a glass-ceramic able to precipitate these crystals.
  • a Perovskite structure such as Li 3 N, LISICON, La 0.55 Li 0.35 TiO 3 , and the like, LiTi 2 P 3 O 12 crystals having a NASICON structure, or a glass-ceramic able to precipitate these crystals.
  • the lithium ion-conductive crystals may be Li 1+x+y (Al q , Ga 1-q ) x (Ti r , Ge 1-r ) 2-x Si y P 3-y O 12 crystals (wherein 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ q ⁇ 1, and 0 ⁇ r ⁇ 1 and for example, 0 ⁇ x ⁇ 0.4, 0 ⁇ y ⁇ 0.6, 0 ⁇ q ⁇ 1, and 0 ⁇ r ⁇ 1, or 0.1 ⁇ x ⁇ 0.3, 0.10 ⁇ y ⁇ 0.4, 0 ⁇ q ⁇ 1, and 0 ⁇ r ⁇ 1). Crystals that do not include grain boundaries impairing conduction of ions may be advantageous in terms of conductivity. For example, a glass-ceramic substantially almost free of pores or grain boundaries that impair conduction of ions may have high ionic conductivity and high chemical stability.
  • Non-limiting examples of the lithium ion-conductive glass-ceramic include lithium-aluminum-germanium-phosphate (LAGP), lithium-aluminum-titanium-phosphate (LATP), and lithium-aluminum-titanium-silicon-phosphate (LATSP).
  • LAGP lithium-aluminum-germanium-phosphate
  • LATP lithium-aluminum-titanium-phosphate
  • LATSP lithium-aluminum-titanium-silicon-phosphate
  • a parent glass with a composition of Li 2 O-Al 2 O 3 -TiO 2 -SiO 2 -P 2 O 5 is thermally treated for crystallization, a main crystal phase of Li i+x+y Al x Ti 2-x Si y P 3-y O 12 (0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1) may be obtained.
  • 0 ⁇ x ⁇ 0.4 and 0 ⁇ y ⁇ 0.6 and in some embodiments, 0.1 ⁇ x ⁇ 0.3 and 0.1 ⁇ y ⁇ 0.4.
  • the pores or grain boundaries blocking conduction of ions refer to a structure that lowers the lithium ion conductivity of the entire inorganic material including lithium ion-conductive crystals to 1/10 or less of the lithium ion conductivity of the lithium ion-conductive crystals of the inorganic material.
  • glass-ceramic refers to a material obtained by thermally treating glass to educe crystalline phases from glass phases in the glass, the glass-ceramic including amorphous solid and crystals.
  • the glass-ceramic may also refer to a material completely phase-transitioned from glass phases to crystalline phases, for example, a material with a 100% by weight of degree of crystallization.
  • the glass-ceramic may include a material having a 100% by weight of degree of crystallization.
  • the glass-ceramic includes nearly zero pores among crystal particles or in a crystal even when fully crystallized 100%.
  • the lithium ion-conductive solid electrolyte includes a large amount of glass-ceramic, a high ionic conductivity may be obtained.
  • the lithium ion-conductive solid electrolyte may include about 80 parts by weight per 100 parts by weight (wt.%) or greater of lithium ion-conductive glass-ceramic, and in some embodiments, about 85 wt.% or greater, or about 90 wt.% or greater to obtain high ionic conductivities.
  • a Li 2 O component in the glass-ceramic may serve as a Li + ion carrier and is an effective component for lithium-ion conductivity.
  • the amount of the Li 2 O component may be about 12%, about 13%, or about 14% based on the total weight of the glass-ceramic.
  • an upper limit in the amount of the Li 2 O component may be about 18%, 17%, or 16%.
  • An Al 2 O 3 component in the glass-ceramic may improve the thermal stability of the parent glass and may improve lithium-ion conductivity by being present as Al 3+ ions in a crystal phase.
  • a lower limit in the amount of the Al 2 O 3 component may be about 5%, about 5.5%, or about 6%.
  • an upper limit in the amount of the Al 2 O 3 component may be about 10%, about 9.5%, or about 9%.
  • a TiO 2 component in the glass-ceramic is an effective component involved in the formation of glass and the crystal phase.
  • a lower limit in the amount of the TiO 2 component may be about 35%, about 36%, or about 37%.
  • an upper limit in the amount of the Al 2 O 3 component may be about 45%, about 43%, or about 42%.
  • a SiO 2 component in the glass-ceramic may improve the melting properties and thermal stability of the parent glass and may improve lithium-ion conductivity by being present as Si 4+ ions in a crystal phase.
  • a lower limit in the amount of the SiO 2 component may be about 1%, about 2%, or about 3%.
  • an upper limit in the amount of the SiO 2 component may be about 10%, or about 7%.
  • a P 2 O 5 component in the glass-ceramic is an effective component involved in the formation of glass and the crystal phase.
  • the amount of the P 2 O 5 component is less than about 30%, glassification may not occur. Accordingly, a lower limit in the amount of the TiO 2 component may be about 30%, or about 32%.
  • the amount of the P 2 O 5 component exceeds 40%, the crystal phase may not be educed from glass, and desired characteristics may not be attainable. Accordingly, an upper limit in the amount of the P 2 O 5 component may be about 40%, about 39%, or about 38%.
  • glass-ceramic When the glass-ceramic has the above-described composition, glass may be easily formed by casting molten glass, and the glass-ceramic in a crystal phase obtained by thermally treating the glass may have a high lithium-ion conductivity of about 1 ⁇ 10 -3 Siemens per centimeter (S ⁇ cm -1 ).
  • the Al 2 O 3 component and the TiO 2 component may be partially or fully substituted with a Ga 2 O 3 component and a GeO 2 component, respectively.
  • a trace of an additional material may be used in a range of amounts that do not seriously deteriorate ionic conductivity.
  • the lithium ion-conductive solid electrolyte may further include a solid polymer electrolyte, in addition to the glass-ceramic.
  • the solid polymer electrolyte may be a polyethylene oxide doped with a lithium salt.
  • the solid polymer electrolyte may include LiN(SO 2 CF 2 CF 3 ) 2 , LiBF 4 , LiPF 6 , LiSbF 6 , LiAsF 6 , LiClO 4 , LiCF 3 SO 3 , LiN(SO 2 CF 3 ) 2 , LiN(SO 2 C 2 F 5 ) 2 , LiC(SO 2 CF 3 ) 3 , LiN(SO 3 CF 3 ) 2 , LiC 4 F 9 SO 3 , or LiAlCl 4 .
  • the solid polymer electrolyte may form a laminated structure with the glass-ceramic.
  • the glass-ceramic may be disposed between a first solid polymer electrolyte and a second solid polymer electrolyte that each independently include a component of the above-listed components.
  • the lithium ion-conductive solid electrolyte may be used as a single layer or a plurality of layers.
  • the operation principle of the lithium air batteries 10 and 20 is as follows. During discharging, lithium ions from the anode 14 produce a lithium oxide by reaction with oxygen from the cathode 13, through the reduction of the oxygen (oxygen reduction reaction: ORR). On the other hand, during charging, the lithium oxide is reduced, while oxygen is produced by oxygen evolution reaction (OER).
  • ORR oxygen reduction reaction
  • reaction mechanism When the electrolyte is a nonaqueous electrolyte, the reaction mechanism may be represented by Reaction Scheme 1.
  • reaction mechanism When the electrolyte is an aqueous electrolyte, the reaction mechanism may be represented by Reaction Scheme 2.
  • air is not limited to atmospheric air, and for convenience, may refer to a combination of gases including oxygen, or pure oxygen gas. This broad definition of “air” also applies to other terms, including “air battery” and “air electrode”.
  • the lithium air battery is available either as a lithium primary battery or a lithium secondary battery.
  • the lithium air battery may have any of various shapes, and in some embodiments, may have a shape like a coin, a button, a sheet, a stack, a cylinder, a plane, or a horn.
  • the lithium air battery may be applicable as a large battery for electric vehicles.
  • alkyl group indicates a completely saturated, branched or unbranched (or a straight or linear) hydrocarbon group.
  • Non-limiting examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, an iso-amyl group, a n-hexyl group, a 3-methylhexyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, and a n-heptyl group.
  • At least one hydrogen atom of the alkyl group may be substituted with a halogen atom, a C 1 -C 20 alkyl group substituted with a halogen atom (for example, CCF 3 , CHCF 2 , CH 2 F, CCl 3 , and the like), a C 1 -C 20 alkoxy group, a C 2 -C 20 alkoxyalkyl group, a hydroxyl group, a nitro group, a cyano group, an amino group, an alkyl amino group, an amidano group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonyl group, a sulfamoyl group, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C 1 -C 20 alkyl group, a C 2 -C 20 alkenyl group, a C 2 -C 20 al
  • halogen atom indicates fluorine, bromine, chloride, iodine, and the like.
  • alkoxy group represents "alkyl-O-", wherein the alkyl group is the same as described above.
  • Non-limiting examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a 2-propoxygroup, a butoxy group, a t-butoxy group, a pentyloxy group, a hexyloxy group, a cyclopropoxy group, and a cyclohexyloxy group.
  • At least one hydrogen atom in the alkoxy group may be substituted with one of the same substituents as described above in conjunction with the above-described alkyl group.
  • the unsubstituted alkenyl group indicates an unsaturated alkyl group having at least one carbon-carbon double bond in the center or at a terminal of the unsubstituted alkyl group.
  • Non-limiting examples of the alkenyl group include an ethenyl group, a propenyl group, a butenyl group, and the like.
  • At least one hydrogen atom in the unsubstituted alkenyl group may be substituted with one of the same substituents as described above in conjunction with the substituted alkyl group.
  • the unsubstituted alkynyl group indicates an alkyl group having at least one carbon-carbon triple bond in the center or at a terminal of the above-described alkyl group.
  • Non-limiting examples of the unsubstituted alkynyl group include an acetylene group, a propylene group, a phenylacetylene group, a naphthylacetylene group, an isopropylacetylene group, a t-butylacetylene group, and a diphenylacetylene group.
  • At least one hydrogen atom in the alkynyl group may be substituted with one of the same substituents as described above in conjunction with the substituted alkyl group.
  • aryl group which is used alone or in combination, refers to an aromatic hydrocarbon containing at least one ring.
  • aryl group is construed as including a group with an aromatic ring fused to at least one cycloalkyl ring.
  • Non-limiting examples of the aryl group include a phenyl group, a naphthyl group, and a tetrahydronaphthyl group.
  • At least one hydrogen atom in the aryl group may be substituted with one of the same substituents as described above in connection with the alkyl group.
  • heteroaryl group indicates a monocyclic or bicyclic organic compound including at least one heteroatom selected from among nitrogen (N), oxygen (O), phosphorous (P), and sulfur (S), wherein the rest of the cyclic atoms are all carbon.
  • the heteroaryl group may include, for example, one to five heteroatoms, and in some embodiments, may include a five- to ten-membered ring.
  • S or N may be present in various oxidized forms.
  • Non-limiting examples of the monocyclic heteroaryl group include a thienyl group, a furyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, a 1,2,3-oxadiazolyl group, a 1,2,4-oxadiazolyl group, a 1,2,5-oxadiazolyl group, a 1,3,4-oxadiaxolyl group, a 1,2,3-thiadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,2,5-thiadiazolyl group, a 1,3,4-thiadiazolyl group, an isothiazol-3-yl group, an isothiazol-4-yl group, an isothiazol-5-yl group, an oxazol-2-yl group, an oxazol-4-yl group, an oxazol-5-yl group,
  • heteroaryl group includes a heteroaromatic ring fused to at least one of an aryl group, a cycloaliphatic group, or a heterocyclic group.
  • Non-limiting examples of the bicyclic heteroaryl group include an indolyl group, an isoindolyl group, an indazolyl group, an indolizinyl group, a purinyl group, a quinolizinyl group, a quinolinyl group, and an isoquinolinyl group.
  • At least one hydrogen atom of the heteroaryl group may be substituted with one of the same substituents as described above in conjunction with the alkyl group.
  • sulfonyl group refers to R"-SO 2 -, wherein R" may be a hydrogen, an alkyl group, an aryl group, a heteroaryl group, an aryl-alkyl group, a heteroaryl-alkyl group, an alkoxy group, an aryloxy group, a cycloalkyl group, or a heterocyclic group.
  • sulfamoyl group may include H 2 NS(O 2 )-, an alkyl group-NHS(O 2 )-, an (alkyl group) 2 NS(O 2 )-aryl group-NHS(O 2 )-, an alkyl group-(aryl group)-NS(O 2 )-, an (aryl group) 2 NS(O) 2 , a heteroaryl group -NHS(O 2 )-, an (aryl group-alkyl group)- NHS(O 2 )-, or a (heteroaryl group-alkyl group)-NHS(O 2 )-.
  • At least one hydrogen atom of the sulfamoyl group may be substituted with one of the same substituents as described above in conjunction with the alkyl group.
  • amino group refers to a group with a nitrogen atom covalently bonded to at least one carbon or heteroatom.
  • the amino group may include, for example, -NH 2 and substituted moieties.
  • amino group also comprises an "alkylamino group” with nitrogen bound to at least one additional alkyl group, and "arylamino” and “diarylamino” groups with at least one or two nitrogen atoms bound to an independently selected aryl group.
  • carbon ring refers to a cyclic group having 5 to 10 carbon atoms, such as a cyclohexyl group. At least one hydrogen atom in the carbon ring may be substituted with one of the same substituents as described above in connection with the alkyl group.
  • At least one hydrogen atom in the alkoxycarbonyl group, arylcarbonyl group, and heteroarylcarbonyl group may be substituted with one of the same substituents as described above in connection with the alkyl group.
  • an equivalent of a material refers to % by weight. For example, when material A is reacted with 2 equivalents of material B, this means that material A and material B react in a weight ratio of 1:2.
  • An electrolyte was prepared by adding 1 M of bis(trifluoromethanesulfonyl)imide (LiTFSI) to a compound of Formula 2 (Compound A).
  • the amount of the compound of Formula 2 (Compound A) was 25 parts by weight based on 100 parts by weight of the total weight of the electrolyte.
  • a hole was punched in the center of a 5 cm ⁇ 5 cm-sized polypropylene-coated aluminum film (having a thickness of 200 ⁇ 2), and was then blocked with a Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 (LATP) (0ATP) and 0and) having a thickness of about 150 ⁇ m, available from Ohara corporation) film by using an adhesive, thereby forming a first aluminum film including an LATP region.
  • LATP Li 1+x+y Al x Ti 2-x Si y P 3-y O 12
  • the protected lithium anode was mounted in a side of a stainless case, and the cathode with a polypropylene separator (Celgard-3501, available from Celgard) having a thickness of 25 ⁇ h was mounted in the side of the stainless case opposite to the anode.
  • a polypropylene separator (Celgard-3501, available from Celgard) having a thickness of 25 ⁇ h was mounted in the side of the stainless case opposite to the anode.
  • the electrolyte solution of Example 1 was injected between the cathode and the anode, a foamed nickel plate was then disposed on the cathode, and a pressing member that allows air to reach the cathode was pushed to fix a cell, thereby completing the manufacture of a lithium air battery.
  • An electrolyte was prepared in the same manner as in Example 1, except that 20 parts by weight of the compound represented by Formula 2 (Compound A) was used.
  • An electrolyte was prepared in the same manner as in Example 1, except that 97 parts by weight of the compound represented by Formula 2 above was used.
  • a lithium air battery was manufactured in the same manner as in Example 2, except that the electrolyte according to Example 3 instead of the electrolyte according to Example 1 was used.
  • a lithium air battery was manufactured in the same manner as in Example 2, except that the electrolyte according to Example 4 instead of the electrolyte according to Example 1 was used.
  • An electrolyte was prepared by adding 1 M of LiTFSI to tetraglyme (TGM).
  • An electrolyte was prepared by adding 1 M of LiTFSI to Compound B.
  • a lithium air battery was manufactured in the same manner as in Example 2, except that the electrolyte of Comparative Example 1, instead of the electrolyte of Example 1, was used.
  • a lithium air battery was manufactured in the same manner as in Example 2, except that the electrolyte of Comparative Example 2, instead of the electrolyte of Example 1, was used.
  • Example 1 The electrolytes of Example 1, Example 3, Example 4, and Comparative Examples 1 and 2 were analyzed by linear sweep voltammetry (LSV).
  • LSV linear sweep voltammetry
  • a Pt electrode as a working electrode, a Pt grid electrode as a counter electrode, and an Ag/AgNO 3 electrode as a reference electrode were immersed in a container containing an electrolyte which is to be measured to form a cell for LSV analysis. Scanning of the cell was performed with a voltage from an open circuit voltage (OCV) to 6.5V (with respect to Ag/Ag + ) at a scanning rate of 1 mV/s to measure a current value.
  • OCV open circuit voltage
  • 6.5V with respect to Ag/Ag +
  • FIG. 3 is a graph of current density with respect to voltage, obtained from the LSV analysis of the electrolyte solutions of Example 1, Comparative Example 1, and Comparative Example 2.
  • the oxidation voltage was highest for the electrolyte of Example 1 and those of Comparative Examples 2 and 1 were lower than that of Example 1 in this stated order, indicating that the electrolyte of Example 1 has higher electrochemical oxidation resistance than that of Comparative Examples 1 and 2.
  • the "electrochemical oxidation resistance” refers to the stability of an electrolyte at a high voltage.
  • electrochemical oxidation resistances of electrolytes according to Examples 3 and 4 were similar to those of the electrolyte of Example 1.
  • chemical oxidation resistance refers to the resistance to oxidation of an electrolyte.
  • the Li 2 O 2 preservation ratio was highest for the electrolyte of Example 1 and those of Comparative Examples 2 and 1 were lower than that of Example 1 in this stated order, indicating that the reactivity with Li 2 O 2 was lowest in the electrolyte solution of Example 1 and highest in the electrolyte solution of Comparative Example 1.
  • the electrolyte solution of Example 1 has a highest chemical oxidation resistance and the electrolyte solution of Comparative Example 1 has a lowest chemical oxidation resistance.
  • the lithium air batteries of Example 2, Example 5, Example 6, Comparative Example 3, and Comparative Example 4 were discharged in an oxygen atmosphere of 1 pressure at 60°C, at a constant current of 0.24 mA/cm 2 to 1.7V (with respect to Li), and then charged at a constant current to 4.2V, and then at a constant voltage of 4.2V to a current of 0.1 mA/cm 2 .
  • the results of measuring voltage with respect to time during the discharging to 1.7V are shown in FIG. 4 .
  • the voltage of the lithium air battery of Comparative Example 3 rapidly reduces with respect to time, while the voltages of the lithium air batteries of Example 2 and Comparative Example 4 are maintained constant longer than Comparative Example 3.
  • the rapid reduction in discharge voltage of the lithium air battery of Comparative Example 3 is attributed to the reaction of Li 2 O 2 produced in the cathode with the electrolyte during the discharging blocks reversible oxidation and reduction of Li 2 O 2 in the electrode.
  • the maintenance of the discharge voltages of the lithium air batteries of Example 2 and Comparative Example 4 is attributed to that suppressed reaction between Li 2 O 2 and the electrolyte improves the oxygen affinity of the electrolyte, and thus facilitates the supply of oxygen to the electrode.
  • an electrolyte for a lithium air battery may include a compound of Formula 1 that includes a fluorine group in a selected position, and thus may have improved oxidation resistance, improved salt solubility, and improved oxygen affinity.

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Claims (13)

  1. Électrolyte de batterie lithium-air, l'électrolyte comprenant un composé représenté par la formule 1 et un sel de lithium :
    Figure imgb0035
     dans lequel, dans la formule 1,
    R1 et R2 représentent chacun indépendamment un atome d'hydrogène, un groupe méthyle, un groupe éthyle, un groupe propyle, un groupe fluorométhyle, un groupe difluorométhyle, un groupe trifluorométhyle, un groupe fluoroéthyle, un groupe difluoroéthyle, un groupe trifluoroéthyle, un groupe tétrafluoroéthyle, un groupe pentafluoroéthyle, un groupe fluoropropyle, un groupe difluoropropyle, un groupe trifluoropropyle, un groupe tétrafluoropropyle, un groupe pentafluoropropyle, un groupe hexafluoropropyle, ou un groupe heptafluoropropyle ;
    R3 à R14 représentent chacun indépendamment un atome d'hydrogène, un groupe méthyle, un groupe éthyle, un groupe propyle, un groupe butyle, un groupe pentyle, un groupe hexyle, ou un groupe heptyle ;
    au moins l'un de R18 et de R19 et au moins l'un de R20 et de R21 représente chacun indépendamment un atome de fluor, un groupe alkyle en C1 à C10 qui est partiellement ou totalement substitué par du fluor, ou un groupe aryle en C6 à C30 qui est partiellement ou totalement substitué par du fluor, et le reste R18 ou R19 est un atome d'hydrogène, un groupe alkyle en C1 à C10 non substitué ou substitué, ou un groupe aryle en C6 à C30 non substitué ou substitué, dans lequel éventuellement R18 et R19 et/ou R20 et R21 forment un cycle C3 à C8 qui est partiellement ou complètement substitué par du fluor ;
    m est compris dans une plage de 1 à 10 ;
    n est compris dans une plage de 1 à 10 ; et
    p vaut 1 à 10, dans lequel m+n+p ≥ 3.
  2. Électrolyte selon la revendication 1, dans lequel au moins l'un de R18 à R21 représente chacun indépendamment un atome de fluor, un groupe fluorométhyle, un groupe difluorométhyle, un groupe trifluorométhyle, un groupe fluoroéthyle, un groupe difluoroéthyle, un groupe trifluoroéthyle, un groupe tétrafluoroéthyle, un groupe pentafluoroéthyle, un groupe fluoropropyle, un groupe difluoropropyle, un groupe trifluoropropyle, un groupe tétrafluoropropyle, un groupe pentafluoropropyle, un groupe hexafluoroproyle, ou un groupe heptafluoropropyle, et le reste R18 à R21 est un atome d'hydrogène, un groupe méthyle, un groupe éthyle, un groupe propyle, ou un groupe phényle,
    dans lequel, éventuellement, R18 et R19 et éventuellement R20 et R21 forment un cycle cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclonorbornane ou bicyclooctane qui est complètement ou partiellement substitué par du fluor.
  3. Électrolyte selon la revendication 1, dans lequel le composé de formule 1 est un composé représenté par la formule 1a ou la formule 1b :
    Figure imgb0036
    dans lequel, dans la formule 1a, R18 à R21 représentent chacun indépendamment un atome de fluor, un groupe alkyle en C1 à C10 partiellement ou complètement fluoré, ou un groupe aryle en C6 à C20 partiellement ou complètement fluoré ; et
    R15, R16, et R17 sont chacun indépendamment choisis pour former un groupe tel que défini pour R1 et R2;
    Figure imgb0037
    dans lequel, dans la formule 1b, R18 à R21 représentent chacun indépendamment un atome de fluor, un groupe alkyle en C1 à C10 partiellement ou complètement fluoré, ou un groupe aryle en C6 à C20 partiellement ou complètement fluoré ;
    R est un atome d'hydrogène ou un atome de fluor ;
    et k est compris dans la plage de 0 à 2.
  4. Électrolyte selon la revendication 1, dans lequel le composé de formule 1 est choisi parmi des composés représentés par les formules 2 à 5 :
    Figure imgb0038
    Figure imgb0039
    Figure imgb0040
     et
    Figure imgb0041
  5. Électrolyte selon l'une quelconque des revendications 1 à 4, dans lequel une quantité du composé de la formule 1 est comprise dans une plage de 15 parties à 97 parties par poids, sur la base de 100 parties par poids d'un poids total de l'électrolyte.
  6. Électrolyte selon l'une quelconque des revendications 1 à 5, dans lequel le sel de lithium est un composé de sulfonimide de lithium.
  7. Électrolyte selon la revendication 6, dans lequel le composé de sulfonimide de lithium comprend du Li(FSO2)2N, du Li(CF3SO2)2N, du Li(C2F5SO2)2N, du LiN(CpF2p+1SO2)(CqF2q+1SO2) dans lequel p et q diffèrent et p et q sont chacun indépendamment un nombre entier de 1 à 20, du LiN((SO2)2CpF2p) dans lequel p est un nombre entier de 1 à 10, du Li(C6F5SO2)2N, du Li(C10F7SO2)2N, du Li(C6F5SO2)(C10F7SO2)N, du LiN(C6F5SO2)(C6F2p+1SO2) dans lequel p est un nombre entier de 1 à 10, ou du LiN(C10F7SO2)(CpF2p+1SO2) dans lequel p est un nombre entier de 1 à 10.
  8. Batterie lithium-air, comprenant :
    une anode ;
    une cathode ; et
    l'électrolyte selon l'une quelconque des revendications 1 à 7.
  9. Batterie lithium-air selon la revendication 8, dans laquelle la cathode est partiellement ou complètement imprégnée de l'électrolyte.
  10. Batterie lithium-air selon la revendication 8 ou 9, comprenant en outre une couche conductrice d'ion lithium disposée entre une anode et l'électrolyte, et une particule inorganique conductrice d'ion.
  11. Batterie lithium-air selon la revendication 10, dans laquelle la particule inorganique conductrice d'ion est un conducteur d'ion métallique actif vitreux, un conducteur d'ion métallique actif amorphe, un conducteur d'ion métallique actif céramique, un conducteur d'ion métallique actif vitrocéramique, ou une combinaison de ces derniers.
  12. Batterie lithium-air selon la revendication 10, dans laquelle la particule inorganique conductrice d'ion est du Li1+x+yAlxTi2-xSiyP3-yO12 dans lequel 0<x<2 et 0≤y<3, du BaTiO3, du Pb(ZrxTi1-x)O3, du Pb1-xLaxZr1-y TiyO3(PLZT) dans lequel 0≤x<1 et 0≤y<1, du Pb(Mg3Nb2/3)O3-PbTiO3, du HfO2, du SrTiO3, du SnO2, du CeO2, du Na2O, du MgO, du NiO, du CaO, du BaO, du ZnO, du ZrO2, du Y2O3, de l'Al2O3, du TiO2, du SiO2, du SiC, du Li3PO4, du LixTiy(PO4)3 dans lequel 0<x<2 et 0<y<3, du LixAlyTiz(PO4)3 dans lequel 0<x<2, 0<y<1 et 0<z<3, du Li1+x+y(Al, Ga)x(Ti, Ge)2-xSiyP3-yO12(Oy, Ge) dans lequel 0<y<1, du titanate de lithium et de lanthane LixLayTiO3, dans lequel 0<x<2 et 0<y<3, du triophosphate de lithium et de germanium, LixGeyPzS, dans lequel 0<x<4, 0<y<1, 0<z<1 et 0<w<5, un verre au nitrure de lithium, LixNy dans lequel 0<x<4 et 0<y<2, un verre de SiS2(LixSiySz), dans lequel 0<x<3, 0<y<2 et 0<z<4, un verre de P2S5(LixPySz) dans lequel 0<x<3, 0<y<3 et 0<z<7, du Li2O, du LiF, du LiOH, du Li2CO3, du LiAlO2, une céramique de Li2O-Al2O3-SiO2-P2O5-TiO2-GeO2, du Li3+xLa3M2O12 dans lequel 0≤x≤5 et dans lequel M est du Te, du Nb, du Zr, ou une combinaison de ces derniers.
  13. Batterie lithium-air selon l'une quelconque des revendications 10 à 12, comprenant en outre un second électrolyte disposé entre l'anode et la couche conductrice d'ion lithium, dans laquelle le second électrolyte est éventuellement un électrolyte polymère solide ou un électrolyte solide inorganique.
EP15169264.7A 2014-05-27 2015-05-26 Électrolyte pour batterie lithium-air et batterie lithium-air contenant celui-ci Not-in-force EP2950380B1 (fr)

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US9991553B2 (en) 2018-06-05
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JP6671717B2 (ja) 2020-03-25
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